EUR 4228 e UBRARl

EUROPEAN ATOMIC ENERGY COMMUNITY - EURATOM

SOLUBILITY OF TERPHENYLS AND OM2 MIXTURES

IN PURE AND TECHNICAL SOLVENTS

by

G. MOSSELMANS and J. NIENHAUS

1969

@

Joint Nuclear Research ,Center lspra Establishment - Italy

Protedion

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'I1lil document was reproduced on the basis of the best available copy.

,. ,.

UR 4228 e

EUROPEAN ATOMrc ENERGY COMMUNITY - EURATOM

EUR 4228 e

SOLUBILITY OF TERPHENYLS AND OM2

MIXTURES IN PURE AND TECHNICAL SOLVENTS by G. MOSSELMANS and J. NIENHAUS

European Atomic Energy Community - EURA TOM Joint Nuclear Research Center - lspra Establishment (Italy) Protection Luxembourg, April 1969 - 56 Pages - 70 FB

The solub~lity of 'terphenyls and OM2

mixture in pure and tech­nical solvents is studied.

Results are presented on curves where the weight percent terphenyl or OM2 versus temperature is plotted.

EUR 4228 e

SOLUBILITY OF TERPHENYLS AND OM2

MIXTURES IN PURE AND TECHNICAL SOLVENTS by G. MOSSELMANS and J. NIENHAUS

European Atomic Energy Community - EURA TOM Joint Nuclear Research Center - Ispra Establishment (Italy) Protection Luxembourg, April 1969 - 56 Pages - 70 FB

The solublity of rerphenyls and OM2

mixture in pure and tech­nical solvents is studied.

Results are presented on curves where the weight percent terphenyl or OM2 versus temperature is plotted

Joint Nuclear Research Center

lspra Establishment - Italy

Protection

MIXTURES 2 ENTS

ABST,RACT

The solubihty of terpheny,ls and OM 2

mixture in pure and tech­

nical solvents is studied.

Results are presented on curves where the wei·ght percent terphenyl or OM

2 versus temperature is plotted.

The resu1lts ,a-Now some considerations about ,the influence of the structure arrd the nature of fundionaI groups on the sohent abi'lity.

Finally a selection of solvent is made for decontamination purposes.

KEYWORDS

SOLUBILITY

TERPHENYLS

SOLVENTS

DIAGRAMS

DECONTAMINATION

CONTENTS

Abstract

0. Scope of investigation

1. Solubility of pure terphenyls

1.1. Solvents and organics used

1.2. Determination of the solubility

1. 3. Results 1.4. Discussion of experimental results 1.5. Choice

2. Solubility of O M2 Mixtures

2.1. 0 M2 used and method 2.2. Results

2.J. Discussion of experimental results

3. Conclusion

4. Acknowledgements

5. Bibliography.

5

Solubility of Terphenyls and OM2 Mixtures in Pure

and Technical Solvents.(*)

Scope of investigation. The organic compounds thought of until now as coolants in nuclear reactors are polyphenyls, usually a mixture of terphenyls.

These materials present serious difficulties for decon­tamination as they are little soluble, chemically stable,

and melt only at elevated temperatures. Literature data (1) (2) on terphenyl solubility are rather scarce; the results given (3) do not furnish more than a base for the development of decontamination procedures. Conse­quently and in order to find a reliable base for the decontamination methods to be prepared, the solubility

of terphenyls had to be examined systematically. The investigation has intentionally been made as broad as could reasonnably be justified even if some of the solvents might probably find no use in later deconta­

mination techniques. This method allowed not only to get information but also helped to solve the following question: how do the solvent properties change within homologue series or when introducing new functional groups into the solvent

molecule? As a result of a demand from our medical service, some oils which might be useful for human skin decontami­nation have been included in the study. After having chosen some solvents among those tested on terphenyls, a study is made on the behaviour of the "OM:2

11 mixture used in reactors. The possibility to produce an emulsion of the poly­phenyls either by treating them with a solvent emulsion or an appropriate solvent shall also be examinated as well as the solubility behaviour of the high boilers, built in the OM2 under reactor operation. Results on these investigations will be reported later.

(*) Manuscript received on 4 November 1968.

6

1. Solubility of pure terphenyls.

1.1. Solvents and organic products used.

The terphenyls used were the isomers pure from

Merck A.G. with the following purity qualifi-

cat ions

0. !J 3 99,9 % o. - t 3

!J 3 97 98 4 f 3 (3-2 % - ~ 3) m. - i"m• -p. !J 3 99,9 % p. - ~ 3 (for scintillation

use)

m. ~ 3 was not purified any further, as the solu­

bility of the mixture as indicated above does not

differ from that of pure m ~ 3 ; indeed the two

components cannot be separated by fractional

cristalliastion from any solvent in the concentra­

tion region (5). The choice of solvents has to be

determined technologically, after their solvent

ability has been tested, from their conventional

behaviour (boiling point, flash point, explosi­

vity, toxicity) and their price.

The eventual corroding properties of a solvent

have not been taken into account, as the items

to be decontamined will be too different chemi­

cally, so that the choice of an appropriate solvent will have to be made on the spot.

As the fouling process is certainly influenced

by chlorine (4) the use of chlorinated solvents

is not possible for materials which have to be used in reactor loops or experiments.

Characterisation of tested solvents is given in

the following tables.

7

TABLE 1

- General characteristics of all solvents tested

- Pure solvents We give only the quality that we have used

- Technical solvents The semi-q~antitative composition is given.

Solr,nl

GROUP AJiIPHATICS

n- HEXANE OCTANE

ISOPAR G

ISOPAR K

ISOPAR M

VASELI~E OIL

GROUP ALICYCLICS

CYCLO-HEXANE

DECALIN

GROUP AROMATICS

BENZENE TOLUENE XYLENE SOLVESSO

100

SOLVESSO 150

H .l N

H B 40

Table I

by T1p• - composition

MERCK FOR C.HROMATOGRAPHY ESSO CHIMICA PETROL FRACTION C.SATURATED.95 % PARAF­

FINES II II

II II

II II

CARLO ERBA

l\TERCK

II

MERCK

"

PETROL FRACTION C.SATURATED.12 % Cg 56 % c10 , 32 % c11 '

PETROL FRACTION C.SATURATED. 26 % 010 , 60 1i c11 , 13 % c12 •

PETROL FRACTION C.SATURATED: all

D A B 6

FOR CHROMATOGRAPHY

FOR S Yff1'HES IS

CRISTALLIZAB LE P.A.

" LAB . REAGENT ESSO CHIMICA AROMATIC PETROL FRACTION =

110/0 Cg, 85 % c9 , 3 % C10

ESSO CHI~ICA AROMATIC PETROL FRACTION: 1 % c,, 73 % c10 , 23 % c11

" II

MONSANTO

AROMATIC PETROL FRACTION= 5 % c9 , 14 % c10 , 30 % c11 , 29 % c12 13 % PARAFFINES HYDROGENATED TERPHENYI.S MIXTURE 18 % 0 - , 3 , 82 % , 3 - H AROMATIC PETROL FRACTION FROM REFORMING•

THERMIP P2 ES'30 CHIMICA 69 % , - METHYLNAPHTHALENE, ~ NAPH­THALENE, 23 % ALKYLNAPHTHALENE + ~ 2

THERMIP LOURDE

GROUP: HETERO­CYCLICS

TETRAHYDRO­FURAN

PYRIDINE

GROUP: CHLORINATE HYDROCARB

Table I

Na nulacturalfd

by

ESSO CHIMICA

r.'IBRC K

II

CARBONTETRA MERCK CHLORIDE

TRICHLORO- CARLO ERBA ETHYLENE

1. 2-DICHLOR MERCK :BENZENE

GROUP: KETONES ACETONE rmRCK

MET HYLE THY CARLO ER BA KETONE METHYL-i­BtJTYLKETON-. II II

ACETYL- MERCK ACETON.2

CYCLO- MSRCK HEXANONE

ACETO- CARLO ERBA PHENONE

I- PHORONE B D H

Typ, - composition

SIMILAR TO THERMIP P2 .

AROMATIC PETROL FRACTION FROM REFORMING PHENANTHRENE, FLUORENE, PYRE NE + ALKY­LATED PH, F., P.,

PURE

FOR CHROMATOGRAPHY

p. A.

PURE

FOR EXTRACTION ANALYSIS

p.A.

PURE

PURE

PURE

PURE

PURE

LAB. REAGENT

Solvent

GROUP: ALCOHOLS

ETHYL-ALCOHOL I•PROPYL-ALCOHOL TERT.BUTY ALCOHOL

n- BUTYL-! ALCOHOL i BENZYL-ALCOHOL

GROUP: ACIDS ACETIC-

ACID

GROUP: ETHERS

DI-I-PROPYL ETHER

DIOXANE ANISOLE

GROUP: ESTERS

ETHYL-ACETATE

I-BUTYL-ACETATE

n- BUTYL-ACETAT

GROUP: AMINES ANILINS

Table 1

Manulacluraled

by

MERCK

MERCK

MZRCK

MERCK

?IIBRCK

MERCK

MERCK

MERCK CARLO ERBA

MERCK

CARLO ERBA

MERCK

SCHUCHARDT

Type - composition

ABSOLUTE

p.A.

FOR CHROMATOGRAPHY

FOR CHROMATOGRAPHY

FOR CHROMATOGRAPHY

p.A.

p.A.

p.A. R.P.

p.A.

R.P.

FOR CHROMATOGRAPHY

p.A.

Table 1

Manufacturated Solv,nl Type - composition

by

GROUP DIVERSE

ACETO MERCK FOR SYNTHESIS NITIHLE

DIMETHYI MERCK PURE FORMAIVIIDE

DIMETHYL B D H LAB. REAGENT SULFOXIDE

CASTOR CARLO ERBA D A B 6 OIL

OLIVE CARLO ERBA VICTUAIB I

OIL : I

I I

'

I I I

I

I

12

TABLE 2

Pure Solvents

Conventional properties and cost

Remarks

1. Flash range :

According ASTM Standard the values are given for

"open cup" (OC) and for "closen cup" (CC)

2. Explosive range

The values are given in volume per cent of vapour in air at 20 oc.

3. Toxicity:

It is given according to SAX toxic hazard rating code :

4. COS t

0 = None 1 = Slight

2 = Moderate 3 = High U = Unknown

Also for pure solvent the cost is given for the technical quality

1 U.C. is equivalent to 1 U.S. $

5. Specific weight is given in g/ ml at 20 oc

Table 2· (PURE SOLVENTS)

Sf)fcific Boiling Fiash E1plosir, ro,icily

Cost Jolr,nl W.ighl Rang, Rang, Rang, Sltin lnhllation Ut:h

JC •c rOOKg.

GROUP : ALIPHATICS

n- HEXANE 0.66 69 -28 o.c ,1.2-6.g 1 1 35 -22 C. C

GRQup: ALICYCLICS

CYCLO- 0 . .778 79-81 17 c.c. 1 .3-8.4 u 2 21 HEXANE

DECALIN 0.88 1 86-195 57 c.c. 1 2 80

GROUP: AROMATICS

BENZENE 0.88 80 -llC.C. 1.4-8.C 3 3 15

TOLUENE o. 87 11 ·1 + 4C.C. 1.3-7.C 2 2 15 XYLENE 0. 86 138-144 25C.C. 1.1-7.C 1 1 15

I GROUP: METERO-

CYCLICS

TETRAHYDRO- o. 89 66 -17C.C. 2.3- . - 3 3 160 FURAN 11. (

PYRIDINE 0.99 114-116 20 c.c. . 8-12. L 2 2 290

GROUP CHLORINATED HYDROCARBOO

CARBONTETRA 1. 59 76-77 3 3 37 CHLORIDE

TRICHLORO-1. 46 87 2 2 30 ETHYLENE

TETRACHLORO 1. 63 120-22 2 2 30 -ETHYLENE

0- DICHLORO BENZENE-

1.30 1 80-83 77 o.c. 3 2 190

GROUP: KETONES

ACETONE 0.79 56 -17, cc. 2.1-13.0 1 2 19 - 9 o.c

METHYL--6.0.C. 1.8-ETHYLKETONE 0. 80 79-80 1 2 76 -7 c.c. 11.

J s,,.cific Boiling Flash [1plosiv,

To,lcity Cost

Solr•nl W.ighl Rang• Rano- R•nff Sltin ,,,,.,,,;o,, ""h JC •c ,oo,c,.

METHYL-i- .o. 80 114-116 24 o.c. 1.2-8.0 2-3 2-3 96 BUTYLKETONE 16 c.c.

ACETYL- 0.97 139 41 o.c. 2 1 1100 ACETON CYCLO-HEXANONE 0.95 155 42 c.c. 2 1 80

ACETO- 1. 03 199-203 105 , , 128 PHENOl'iE i-PHORONE 0.92 215 96 0. C, 3 3 500

GROUP: ALCOHOLS

ETHYL 0.79 78 16 o.c. 3.3-19 1 2 48 ALCOHOL 14 c.c.

i- PROPYL 0.79 82 22 o.c. 2.0-5.2 1 2 410 ALCOHOL 12 c.c. t ert. BUTY.~ o. 78 83 9.c.c. 2. 3-8 2 2 64 ALCOHOL

n-BUTANOL o. 81 11 8 35 c.c. 1. 4- 2 2 72 40 o.c. 18 ..

BENZYL 1.04 206 101 c.c. 1 1 108 ALCOHOL

GROUP ACIDS

' ACETIC 1. 05 11 8 40 C. C 3 3 48

ACID

GROUP ETHERS

DI-i-PRO- 0.72 68 -28cc 1. 4-21 3 2 120 PYL-ETHER

DIOXAN 1. 04 101 1 1 c.c. 1. 9-22 2 3 160 ANISOL 0.996 154 52 o.c. 2 3 320

I

Sp,cific Boiling Flash ro,icit1

1ptosiv1.__ _____ -. Coit Wtight Rang, Rang,

JC •c Ran,. 5 ... ,.,, ,,,,....,_.,, ut: I

.. '

1

··- 1,00,cg.

GROUP: ESTERS ETHYL- 0.90 77 -5 c.c. , 2-11. 1-2 2 42 ACETATE +7 o.c.

n- BUTYL o.88 126 23 c.c. , 7-15 1 1- 2 80 ACETATE 34 o.c. i- 'UTYL ACE ATE o .. 87 117 17 c.c. 2 2 160

GROUP: AMINES ANILINE 1. 02 184 76 c.c. 3 3 140

GROUP: DIVERSE ACETO- 0.79 82 6.0.C. 3 3 270 NITRILE DIMETHYL ·o. 95 152-155 67 o.c 2.2- 3 2 140 FORMAMIDE 15,2

DIMETHYL 1. 10 DECOMP 90 o.c u u 400 SULFOXYDE 100 °

I

I

I

I I I

I '

TABLE 3

T:ECHNICAL SOLVENTS

Conventional properties and cost Remarks.

1. Molecular weight :

It is given as the average value For the explanations of the other columns see table 2

rab/e ] ~ T=CWJICAl SOLVE~JTS)

~ltcular Sp,cllic Boiling Solv,nt

Flash Eiplos,r, roiicll1

w,lght W.lghl Rang, Rang• R1,ng1 Sltin hhlllllion •c •c

GROUP: ALIPHATICS

OCTANE 1 1 4 0.73 116-121 It. 1 oc. 1-6 1 2

ISOPAR G 13 8 0.75 159-179 40 c.c. 1 1

ISOPAR K 156 0.76 176-95 52 C. C. 1 1

ISOPAR M 177 o. 7 8 206-47 80 c.c. 1 1

VASELINE 430 o. 89 > 360 1 C OIL

GROUP: AROI/lATICS SOLVESSO 13 8 0. 87 160-75 48 o.c. 1-6 1-2 1-2

100 SOLVESSO 13 8 o. 89 1 87-212 150

66 o.c. 1-6 1-2 1-2

HAN 0.93 181-281 58 o.c. 1-2 1-2

H B 40 1\.,245 1. 005 345 174 c.c u u 1 80 0. C

THERMIP 153 0.99 230-60 ~lCOC.C u u P2 12 80. C

THERMIP LOURDE 1. 006 > 260 > 100 u u

AKJ> - M 206 1. 07 327-72 178 c.c. u u 20 8 0. C

GROUP: DIVERSE

CASTOR 850 0.97 313 230.c.c. 1 1 OIL

OLIVE 790 0.91 225 o.c 0 0 OIL

Cost

u~ ,ool(,

35 40 40

39

60

34

34

3, 71

32

32 32

96

80

17

1.2. Determination of the solubility.

A weighted (or measured) amount of solvent is added to a weighted quantity of terphenyl; both are heated

together until producing a clear solution which

then is cooled. A preliminary test gives an indication on the tempe­

rature where crystallisation begins. After reheating until a clear solution is obtained (control of weight), cooling is restarted slowly (cooling rate~ 1 min. 0 c-1 ) while stirring with the thermometer and eventual seeding of single large

crystal easily distinguishable. The temperature where the first crystal appears thus

exactly can be determined. This point is the satu­ration point of the solution at the determined tempe­

rature. The known concentration together with the temperature which has been measured gives one point of the solu­

bility curve. By addition of further quantities of solvent the con­

centration changes and a new point of the curve is

determined as described above. One point of the solubility curve is the fusion point

of pure terphenyl (c= 100 % ~ 3). The curve then down to room temperature (20 oc) is determined experimen­

tally as described above. The weight per cent versus temperature oc is plotted

on the solubility curves. This method is described (7) as the synthetic method to determine solubility : for a known concentration is checked the temperature, where a 2- phase system becomes in I-phase system etc ••

18

The term weight per cent means g terphenyl in

100 g solution. If the reader wants to get

information on the solubility per g terphenyl in

100 g of solvent,-an other usual unit,-he can cal­

culate it using the following formula

S g ~ 3 = Jo X 100 ( 1) 100 g solvent 100 - %

The amounts used depend on solubility.

The mass of terphenyl and solvent together has been

chosen large with respect to the thermometer mass;

the combined mass further must not be too small in

order to get constant cooling velocities.

All results have been taken from experiments with

at least 100 g total mass.

Weights have been determined with a Mettler balance

(maximum 800 g), division of scale O,l g). The

smallest quantity of terphenyl used in case of bad

solubility was 3 g. The maximum error of weighing (0,05 g difference

are discernible) is thus 1,5 % ... The thermometers used (1/1° scale graduation) were

calibrated.

1. 3. Results.

The curves are given according to the solvent list

of table 1.

19

Solubilit~ curves.

On the solubility curves are pl~tted weight-%~ 3

versus temperature for every solvent tested.

Two different scales are used : one for the

solubility of o - and m - 0 3 up to a "solution"

of 100 % 0 3 = meltinR point of pure 0 3 : another up to 5 or 10 % n- 0 3 resoo.~tively,

due to the very different solubility of the

P - 0 3.

45

T A B L E 4

SOLVENTS ARRANGED ACCORDING TO THEIR SOLVENT ABILITY.

Remarks :

An artificial {o - solvent ability given in the table (first column) was introduced for the following reason:

In several cases the difference of the solubility between near !'.elated solvents considered only at one temperature are in the range of experimental error. Such values cannot

be taken as the basis of discussion for solubil:ity rules. To overcome this difficulty and to correct the wrong impression one can have, looking only to one point of the curve and without consideration for the form and the slope of the curves, we tried to classify the solvents by an artificial solubility- number. We took from the curves the solubility-values of o-, m-, and p- % 3 for every solvent at 25 °c and 50 °c. The sum of this six values for one solvent is our solubility- number with the dimension S:. of g o-, m-, p- t 3 at 25 oc and 50 °c in 600 g solution-. We assumed it to be 100 for benzene as reference solvent and received in this manner our fo- solvent ability. Practically with this operation we made a first step of integration of the 3 curves and in fact we found it to be sufficient to arrange the solvents in a logical way with respect to their solvent power. With the addition of the values oft.he 3 terphenyls we can expect a better elimination of the experimental error because ~t is unlikely that the experimental error is in the same direction for all 3 terphenyls. The addition of the values at two different temperatures takes into account in first approximation also the form and the slope of the curves.

Table 4

.,, Solvtnt WEIGHT-0/o

a1t1u1, Solvent O•• rn--. ,-,. • 2s•c so• c 2s•c so•c zs0 c so• c

,07.5 TETRAHYDROFURAN 82. 0 96.0 55.0 73.0 2.75 5.50

104.3 DIOXANE 80.5 96.0 51.0 72,0 1. 60 3. 12

101. 0 PYRIDINE 79.0 96.0 44.0 71. 0 1. 80 4.10

100 BENZENE 80.5 96.5 43.5 67.5 1.35 3.25

98. 8 CYC LOHEXANONE 76.0 94.5 44.5 69,0 1. 65 3,70

97.5 DIMETHYLFORMAMIDE 77.5 96.0 41. 0 67.0 , .·oo 2. 80

96.6 METHYLETHYLKETONE 76.0 97.0 3 8. 0 69.0 o.88 2.00

93 I 7 ACETONE 77. 0 96.0 30.0 69.0 0.60 1. 50

93.4 ANISOLE 75.0 95,5 32.0 66.5 1. 40 3. 15

92.8 TOLUENE 75.0 96.5 31. 5 65.0 1 • 16 2.68

90.6 ACETOPHE~ONE 69.0 93,5 36.5 62,5 , • , 0 2.50

88.6 ETHYLACETATE 76.5 95.0 25,0 61.0 o. 5 8 1. 40

88. 3 XYLE11ffi 71. 0 95.0 27,5 61. 5 o. 85 2.27

87.9 ACETYLACETONE 70.0 95.0 27.0 63. 0 0.70 1. 65

87. 7 ANiLINE 74.5 95.5 24.5 60.0 o. 5 8 1. 60

87. 5 i-PHORONE 63.0 92.5 36.0 60.0 1 • 1 5 2.35

87. 1 THERMIP P 2 70.0 92.0 31. 5 57,5 1. 35 2.65

86. 6 TR!CHLOROETHYLENE 6 8. 0 92.5 31. 5 5 8. 5 0.94 2.22

86.5 ACETONITRIL 74.5 97.5 1 0. 5 70.0 0.20 0.54 86. 1 NillTHYL- i-B UTYL- 70.0 95.0 24.5 60.5 0.50 1. 52 KETONE 85. 8 o-DICHLOROBENZENE 67.5 94,0 30.0 56.0 1 • 10 2.50

84. 0 SOLVESSO 100 70.0 94.0 22.5 56.0 o. 84 2.00

83. 5 n-BUTYLACETATE 6 8. 5 95.0 22.5 56.0 0.66 1.50 82. 1 H A N 6 8. O 92.5 24.0 53. 0 0.75 1. 90 a,. s SOLVESSO 150 69.0 93,5 21. 5 52.5 o. 80 1. 95 80. 8 THERMIP LOURDE 62.5 92.0 2 8. 0 50.0 1. 35 2.60 80. 5 i-BUTYLACETATE 67.0 94.0 17.0 56.0 0.50 1. 20 Bo. o CARBONTETRACHLORIDE 65.0 93.0 20.0 54.5 0.42 1 • 1 4

78. 0 CYCLOHEXANE 68. 0 96.0 12.0 51. 5 0.,2 0.70 75.8 AKP-M 55.0 88.5 2 8. 5 45.0 1. 90 2,95 74,2 TETRACHLOROETHYLENE 5 8. 5 91. 0 19.0 47.0 o. 36 1. 20

73.4 HB - 40 51.0 87. 5 29.5 44.0 0.90 1. 83

72.4 DECALIN 61. 0 94.0 12.5 43.5 0.26 0.70 72.0 DI~ETHYLSULPHOXIDE 51. 5 97.0 15.5 45.0 0.54 1.04

.,. Solvent

attmt,

66.1 60.4 55.7 52. 1 49.4 46.3 45.8 42.8 41. 9 41. 6

'! 0. 1 J9.7 3 8. 0 33.9 31. 9

Table ,

WE IGHT-0/o

Solvent O··· m--. P--1 2s•c so• c 2s• c so 0 c 2s• c so• c

DI-i-PROPYL ETHER 60.0 95.0 7.5 3 o. 0 0.20 0.52 BENZ YL ALCOHOL 40.0 94.0 10.0 3I. 5 o. 3 5 0.90 n-HEXANE 36.0 97,5 5,5 23. 5 0.11 0.56 OCTANE 27,5 97.0 5.0 22.5 0.12 0.45 ACETIC ACID 32.5 93. 5 5,5 17. 5 o .. 14 0.33 OLIVE OIL 24,5 77,5 12.0 20.5 o. 3 8 0.65 ISOPAR G. 21. 0 93. 0 4.5 14.0 o. 11 o. 30 ISOPAR K 16.5 92.0 3. 5 '13. 0 0.10 0.25 ISOPAR M 15.0 92.0 4.0 11. 5 0.08 0.28 n- BUTANOL 12.5 93. 0 4.0 12.0 0.12 0.30 ETHANOL 11. 5 94.5 3.0 8.0 0.08 0.20 t- BUTANOL 9.5 95.0 2.0 9.5 0.08 0.18 i- PROPANOL 8.0 95.0 2.0 6.0 0.06 0.16 VASELIN OIL 13.0 70.0 4.5 11. 0 0.20 00"36 CASTOR OIL 15.0 52.5 7.5 17.5 0.28 o. 52

48

1.4. Discussion of experimental results.

In table 4, the compounds are classified according

to their solvent ability for terphenyls. These data·

indicate the following relations between molecular

structure and solvent ability.

a- Benzene is the fundamental aromatic compound.

We propose thus to adopt his solvent ability to

be 100 % b- Only heterocyclic compounds solve better than

benzene.

example : Tetrahydrofurane - Dio~ane - Pyridine.

~- The substitution of hydrogen in the benzene

nucleus decrease the solvent ability from little

changing to large one according to the following

substitutions.

H substituted by an ether group

H substituted by (an)alkyl groups:

H substituted by an chlorine 11

H substituted by an amino group

H substituted by an hydroxyl"

Benzene_., Anisole

Benzene _ 7 Xylene

Benzene --9Di chlo benzene

Benzene.-. Aniline

Toluene-,'> Benzyl alcohol

d- The higher the degree of substitution the more de­creases the solvent ability

example : Toluene, Xylene, Solvesso.

e- The hydrogenation of the nucleus results in a

decrease of the solvent ability similar to that

which occurs by the substitution of H by amino and

hydroxyl groups.

example : Benzene - Cyclohexane Thermip - Decalin

f- For aliphatic and alycyclic hydrocarbons the solvent

ability generally decreases simultaneously with the

molecular weight example Hexane - Vaseline Oil

Cyclohexan - Decalin

For compounds with a similar number of C. atoms, the

alicyclic hydrocarbons solves better than

49

the aliphatic one

example : Hexane - Cyclohexane

g- In comparison to the hydrocarbons of the aliphatic and alicyclic series, the introduction of oxygen increase

the solvent ability in the following line :

i) ether bound ii) ester bound

iii) Keto bound

The introduction of oxygen as OH group decreases, at least for the low-molecular weight compounds, the solvent ability of the hydrocarbons.

1.5. Choice. We have selected to teet and use for decontamination

purposes following solvents ALIPHATICS AROMATICS

KETONES

HETEROCYCLICS ETHERS ESTERS

ISOPAR G BENZENE THERMIP SOLVESSO 150 ACYCLOHEXANONE METHYETEYKE'.i:ONE

ACETONE

TETRAHYDROFURAN DIOXANE ETHYLACETATE

This selection is made on the base of the experi­mental results in comparison with the conventional

properties and the price ( table 1 to 3 ).

If Benzene, Tetrahydrofuran and Dioxane remain in this selection it is only due to their excel­

lent ability to solve terphenyls.

50

2. Solubility of OM2

mixtures.

2.1. To complete our investigations for practical

decontamination purposes we have determined

the solubility of OM2 mixtures in the solvents

selected in part. 1.

The OM2 mixture we have used were prepared

by us from the three pure terphenyls following

the average composition of OM2

p. ~ 3 5 1o m. ~ 3 75 /o o. ~ 3 20 %

This procedure we used in order to avoid sampling

errors.

The method used to measure the solubility is the

same as descripted in part. 1., this means deter­

mination of the temperature where crystallization

begins. The measured temperature indicates the point

where the mixture solvent-OLl2 is liquid.

After the crystallization-poi~t is reached,

we have practically a fractional crystallization

of the components of OM2 mixture.

This p-Enomeno~ 15 of no interest for decontami­

nation work, because we have to work in the total

liquid range. 2.2. Results.

Results are presented in the following curves.

The values obtained for the "sy!'lthetic OM2 mix­ture" were controlled using OM2 tech!1ical grade

manufactured by· PROGIL.

The relative difference in the solubility of two mixtures is in the range of! 5 {o for temperatures

from 25 °c to 80 °c.

54

2.3. Discussion of experimental results.

According to the curves the solubility of O M2 mixtures is about the half of the solubility of the pure m. terphenyls.

For O M2 we find the same classification of solvent in respect of their solvent ability as given table 4.

3. Conclusion.

From experimental results and in comparison with the conventional behaviours and the price we had finally choosen the following solvents for ourdecontamination

purposes: ISOPAR G SOLVESSO 150

THERMIP ACETONE METHYLETHYLKETONE

Isopar G is take in account only for his inerty in front of the isolated electrical components. This choice has been confirmed by preliminary decon• tamination tests with success. Decontamination techniques based on the use of this solvents are under study. For skin decontamination, our medical service recom­mand the following solvent mixtures=

80 % METHYETHYLKETONE + 20 ~ OLIVE OIL + eventual local anesthetic agent.

4. Acknowledgements.

The authors acknowledge with thanks the discussions with and advice from Mr F.Geiss (Chemistry Depart­ment).

Thanks are also due to Mr. Hannaert, Chief of Organic Chemistry Service.

55

·Bibliography.

(1) Organic coolant Data book

Tech. Publ. N° AT - 1 July 1958 Mosanto Chemical comn, St Louis.

(2) E. E. Mc. Langlin, H.A. Zainal;

- Solubility Behaviour of Aromatic Hydrocarbons in benzene.

J. Chem. Soc. 1959 p- 863 - 867 - Solubilit~es in Carbon Tetrachloride.

J. Chern. Soc. 1960 n- 2485- 488 (3) .R.T. Keen

Solubility of terphenyls at room temperature

NAA - SR - Memo 2412 (1958)

(4) B. VERSINO ed al. Analisi delle rniscelle organjche sostitute dei terfenili

(in press) Ispra 1967. (5) H. KIENITZ

Bestimmung der Loslichkeit in HOUBEN-WEYL - Band III/ lp. 219 - 254

General literature.

- C. MARSDEN Solvents guide CLEVER - HUNE PRESS 1962 London

- N. Irving Sax Dangerous properties of indutrial materials Reinhold Publishing Coprporation 1963 New York.

- Technical Information about solvents.

ESSO.CHIMICA - Uilano -- HOUBEN WEYL - Methoden der Organischen Chemie

THIEME VERLAG 1959 - Stuttgart.

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